Methods of forming molybdenum sputtering targets

ABSTRACT

In various embodiments, sputtering targets are formed by introducing molybdenum powder into a sheet bar mold, pressing the powder to form a sheet bar, sintering the sheet bar to form an ingot having a density of at least 90% of a theoretical density, preheating the ingot, rolling the ingot to form a plate, and heat treating the plate.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to forms of molybdenum, their use assputtering targets and method of their manufacture.

BACKGROUND OF THE INVENTION

The sputtering technique is a film-forming technique with which a plasmais utilized to generate ions striking a sputtering target so as toresult in atoms of the sputtering target depositing on a substrate as afilm. The sputtering technique is particularly used to produce ametallic layer in various manufacturing processes used in thesemiconductor and the photoelectric industries. The properties of filmsformed during sputtering is related to the properties of the sputteringtarget itself, such as the size of the respective crystal grain and theformation of secondary phase with distribution characteristics.

Various sputtering techniques are used in order to effect the depositionof a film over the surface of a substrate. Deposited metal films, suchas metal films on a flat panel display device, can be formed by amagnetron sputtering apparatus or other sputtering techniques. Themagnetron sputtering apparatus induces plasma ions of a gas to bombard atarget, causing surface atoms of the target material to be ejectedtherefrom and to be deposited as a film or layer on the surface of asubstrate. Conventionally, a sputtering source in the form of a planardisc or rectangle is used as the target, and ejected atoms travel alonga line-of-sight trajectory to deposit on top of a wafer whose depositionface is parallel to the erosion face of the target.

However, a tubular-shaped sputtering target can also be used. In thiscase, the plasma is external and the atoms are sputtered from theexterior of the tube. The flat substrate is slowly passed over thetarget. Typically, its motion is horizontal, and in a direction at aright angle to the target axis, which is also horizontal. Thus thesubstrate can be gradually coated as it passes over the target.

In many cases, sputtering targets, particularly those containingmolybdenum, have a wrought microstructure with non-uniform graintexture, which may change from one sputtering target to the next. These“non-uniformities” lead to non-uniform films being deposited ontosubstrates and devices, particularly flat panel displays that do notoperate optimally.

In other cases, molybdenum-based sputtering targets are manufacturedusing a conventional thermomechanical working step. Unfortunately, thismethodology generally induces heterogeneity of grain size and texture.The heterogeneity in the sputtering targets typically leads to sputteredfilms that do not possess the uniformity desired in most semiconductorand photoelectric applications.

In some applications, large plates of pure molybdenum are required assputtering targets. In such cases, the production of large plates isaccomplished through the machining and assembly of multiple plates,often referred to as segmented plates. The preparation of segmentedplates requires an increased amount of machining and assembly costcompared to the production of a single plate ingot. Additionally, theassembly of different plates creates variability in the large segmentedplate, which can cause unacceptable variability in films formed bysputtering the large plate target.

Therefore, there is a need in the art for molybdenum sputtering targetsthat overcome the deficiencies of the prior art and have a fine grainsize and uniform grain texture.

SUMMARY OF THE INVENTION

The present invention is directed to molybdenum, sputtering targetscharacterized as having no or minimal texture banding or throughthickness gradient. The molybdenum sputtering targets having a fine,uniform grain size as well as uniform texture, have high purity and canbe micro-alloyed to improved performance.

The present invention is additionally directed to a tubular-shapedsputtering target formed by:

-   A) placing molybdenum powder in a mold and pressing the powder at a    pressure of from 200 to 250 MPa and sintering the pressed piece at a    temperature of from 1780 to 2175° C. to form a billet;-   B) removing the center of the billet to form a tubular billet having    an inner diameter ID_(l) and an outer diameter OD_(l);-   C) working the tubular billet to form a worked billet having an    inner diameter ID and an outer diameter OD_(f) such that the ratio    of OD_(l) to OD_(f) is at least 3:1; and-   D) heat treating the tubular billet at a temperature of from 815 to    1375° C.

The present invention is also directed to a tubular-shaped sputteringtarget containing molybdenum having a uniform texture, which featuresparticularly a 110 orientation parallel to the longitudinal directionand a 111 orientation relative to the radial direction.

The present invention is additionally directed to a method of making atubular sputtering target that includes:

-   A) placing molybdenum powder in a mold and pressing the powder at a    pressure of from 200 to 250 MPa and sintering the pressed piece at a    temperature of from 1780 to 2175° C. to form a billet;-   B) removing the center of the billet to form a tubular billet having    an inner diameter ID_(l) and an outer diameter OD_(l);-   C) working the tubular billet to form a worked billet having an    inner diameter ID and an outer diameter OD_(f) such that the ratio    of OD_(l) to OD_(f) is at least 3:1; and-   D) heat treating the tubular billet at a temperature of from 815 to    1375° C.

Embodiments of the present invention are directed to a disc-shapedsputtering target formed by:

-   -   I) placing molybdenum powder in a mold and pressing the powder        at a pressure of from 200 to 250 MPa and sintering the pressed        piece at a temperature of from 1780 to 2175° C. to form a billet        having a diameter of D_(o);    -   II) extruding the billet to form an extruded billet having a        diameter of D₂ such that the ratio of D_(o) to D₂ is from 3:1 to        5:1;        -   III) applying a first heat treatment to the extruded billet            at a temperature of from 900 to 1300° C.;    -   IV) upset forging the extruded billet at a temperature of from        870 to 1200° C. to form a forged billet having a diameter D_(f)        such that the ratio of D_(f) to D₂ is from 1.5:1 to 3:1; and    -   V) applying a second heat treatment to the forged billet at a        temperature of from 1200 to 1400° C.

Embodiments of the invention are also directed to a disc-shapedsputtering target containing molybdenum having a uniform grain andtexture.

Other embodiments of the invention are directed to large molybdenumplates having a non-segmented construction, weighing at least 300 kg,and containing at least 99% by weight of molybdenum.

Additional embodiments of the invention are directed to a process forpreparing the above-described plates, which includes the steps of:

-   i) pouring powder into a sheet bar mold;-   ii) consolidating the powder by cold isostatic pressing (C.I.P.) at    a pressures of from 100 to 250 MPa (15 to 36 ksi) to form a sheet    bar;-   iii) sintering the sheet bar at a temperature of at least 1600° C.    to form an ingot having a density of at least 90% of the theoretical    density;-   iv) preheating the ingot at a temperature of from 1100 to 1450° C.;-   v) hot rolling the ingot at a temperature of from 1050 to 1400° C.    to effect a reduction in the thickness and an increase in the length    of the ingot; and-   vi) heat treating the rolled ingot at a temperature of from 850 to    950° C.

The present invention is further directed to sputtering targets andsintering tiles that include the above-described molybdenum plate.

The present invention is additionally directed to a method of sputteringthat includes subjecting any of the above-described sputtering targetsto sputtering conditions and thereby sputtering the target.

The present invention is further directed to a method of sputtering thatincludes subjecting the above-described sputtering target to sputteringconditions and thereby sputtering the target.

The present invention is further directed to a method for making a thinfilm including the steps of:

-   (a) sputtering the above-described sputtering target;-   (b) removing Mo atoms from the target; and-   (c) forming a thin film comprising molybdenum onto a substrate.

The present invention also provides a thin film made in accordance withthe above-described method. The thin films can be used in electroniccomponents such as semiconductor devices, thin film transistors, TFT-LCDdevices, black matrix devices that enhance image contrast in Flat PanelDisplays, solar cells, sensors, and gate device for CMOS (complementarymetal oxide semiconductor) with tunable work functions.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of a consolidated hollow billet according tothe invention;

FIG. 2 is a schematic view of a hollow billet being extruded accordingto the present invention for extrusion of a tube;

FIGS. 3A, 3B and 3C show electron backscatter diffraction (EBSD)electron micrographs relative to the longitudinal (z), radial (ND) andtangential (x) directions, respectively, of a tubular sputtering targetaccording to the present invention;

FIG. 4 shows the EBSD micrograph of 3B under higher magnification;

FIG. 5 shows the EBSD Pole Figure analysis of a tubular sputteringtarget according to the present invention;

FIG. 6 shows the EBSD Inverse Pole Figure analysis of a tubularsputtering target according to the present invention;

FIG. 7 is a schematic showing a solid billet being extruded according tothe invention for intermediate work pieces;

FIGS. 8A and 8B show schematic views of upset forging a billet accordingto the present invention;

FIGS. 9A and 9B show sputtering target plates according to the presentinvention being cut from forged billets; and

FIGS. 10A and 10B show a billet being hammer forged according to oneembodiment of this invention.

DETAILED DESCRIPTION OF THE INVENTION

Other than in the operating examples or where otherwise indicated, allnumbers or expressions referring to quantities of ingredients, reactionconditions, etc., used in the specification and claims are to beunderstood as modified in all instances by the term “about.” Variousnumerical ranges are disclosed in this patent application. Because theseranges are continuous, they include every value between the minimum andmaximum values. Unless expressly indicated otherwise, the variousnumerical ranges specified in this application are approximations.

As used herein, the term “banding” refers to non-uniformities in thegrain or texture, the grain size, or grain orientation that occur in astrip or pattern along the surface of the sputtering target. As usedherein, the term “through thickness gradient” refers to changes in grainor texture, grain size, or grain orientation moving from the edge of thetarget to the center of the target.

The forms of molybdenum, sputtering targets described herein below arecharacterized as having no or minimal banding or through thicknessgradient. As such, the present invention is directed to molybdenumsputtering targets having fine, uniform grain size as well as uniformtexture, substantially free of both texture banding and throughthickness gradient from a center to an edge of the target, with highpurity and optionally micro-alloyed for improved performance.

In the present invention, the molybdenum sputtering targets are verypure, as such, the molybdenum sputtering targets have a purity of atleast 99.5%, in some cases 99.9%, n other cases 99.95%, in someinstances at least 99.99% and in other instances at least 99.999%. Asused herein, the term “purity” refers to the weight percentage ofmolybdenum in the sputtering target.

The present invention provides a tubular-shaped sputtering target andits method of manufacture. The present method involves the use of puremolybdenum powder as a starting material, and its consolidation to asubstantially fully dense article in the form of a tube. The tubularform produced has a fine, uniform grain size, and a texture which issubstantially uniform throughout, and does not change from tube to tube.Such tubular forms yield thin films that have the required purity, and athickness which is both easily predictable and uniform across the areaof a given substrate.

In an embodiment of the invention, the tubular-shaped sputtering targethas a texture that is substantially free of banding and substantiallyfree of any through thickness gradient.

According to the present invention, a tubular-shaped sputtering targetis formed by the pressing and sintering of molybdenum powder to form abillet, removing the center of the billet, working the billet, and heattreating the billet to form a tubular-shaped sputtering target.

In the present invention, ammonium dimolybdate is selected to meetrequired purity specifications, and then reduced to molybdenum metalpowder in hydrogen using conventional hydrogen reduction processes. Theammonium dimolybdate can be at least 95% pure, in some cases at least99% pure, in other cases at least 99.5% pure and in certain instances99.999% pure. The purity of the ammonium dimolybdate can range betweenany of the values recited above.

Typically, the molybdenum powder is placed in a mold and the powder ispressed at a pressure of at least 16 ksi, in some cases at least 30 ksiand in other cases at least 32 ksi. Also, the powder can be pressed at apressure of up to 40 ksi, in some cases up to 37 ksi and in other casesup to 35 ksi. The molybdenum powder in the mold can be pressed at anypressure recited above or at pressures ranging between any of thepressures recited above.

Further, when the pressed billet is sintered in the mold, it is sinteredat a temperature of at least 1785° C., in some cases at least 1800° C.and in other cases at least 1850° C. Also, the pressed billet can besintered at a temperature of up to 2200° C., in some cases up to 2175°C. and in other cases up to 2150° C. The pressed molybdenum billet inthe mold can be sintered at any temperature recited above or attemperatures ranging between any of the temperatures recited above.

In an embodiment of the invention, the pressing is performedisostatically. In another embodiment of the invention, the powder issintered in hydrogen.

As shown in FIG. 1, the center of the consolidated billet is removedthrough trepanning such that the ID_(l) is smaller than the insidediameter of the finished tubular form. The OD_(l) is selected such thatthe ratio of reduction in cross-sectional area normal to the billetlength is at least 3:1, in some cases at least 3.5:1 and in other casesat least 4:1. Also, the reduction in cross-sectional area normal to thebillet length can be up to 12:1, in some cases up to 10:1 and in othercases up to 8:1. In a particular embodiment of the invention, thereduction in cross-sectional area normal to the billet length is 4.9:1or higher. The reduction in cross-sectional area normal to the billetlength can be any of the values or range between any of the valuesrecited above.

The tubular billet is worked to form a worked billet having an innerdiameter ID and an outer diameter OD_(f) such that the ratio of OD_(l)to OD_(f) is as described above.

In an embodiment of the invention, the tubular billet is worked byextruding the billet, as shown in FIG. 2. In this embodiment, the billetis extruded with a reduction ratio (created by the change of OD_(l) toOD_(f)) in cross-sectional area as described above. The billet lengthmay be variable. The product form ID is controlled through the use ofmandrel tooling.

In a particular embodiment of the invention, the tubular billet can beextruded at a temperature of at least 925° C., in some cases at least950° C., and in other cases at least 1000° C. Also, the tubular billetcan be extruded at a temperature of up to 1370° C., in some cases up to1260° C. and in other cases up to 1175° C. The tubular billet can beextruded at any temperature recited above or at a temperature rangingbetween any of the temperatures recited above.

In another embodiment of the invention, the working, i.e., reductionratio (created by the change of OD_(l) to OD_(f)) in cross-sectionalarea, is achieved through a rotary forging process that replaces theextrusion.

In an embodiment of the invention, after working the billet, it is heattreated at a temperature of at least 815° C., in some instances at least925° C., in some cases at least 950° C. and in other cases at least1000° C. Also, the heat treatment can be carried out at up to 1375° C.,in some cases up to 1260° C. and in other cases up to 1175° C. The heattreatment can be at any temperature or range between any temperaturesrecited above.

In a particular embodiment of the invention, the heat treatment iscarried out at from 1250 to 1375° C.

In another particular embodiment of the invention, the heat treatment iscarried out at from 815 to 960° C.

-   -   While not wishing to be limited to any single theory, under some        heat treatment conditions, it is believed that subjecting the        extruded tubular form to heat treatment results in        recrystallization, yielding a strain-free, equiaxial grain        structure.    -   However, in some embodiments of the invention, the heat        treatment is applied for “stress-relief” purposes only.    -   After heat treatment, the tubular form is machined to its final        dimensions. In an embodiment of the invention, the        tubular-shaped sputtering target has a uniform texture which is        a 110 orientation parallel to the longitudinal direction and a        111 orientation relative to the radial direction. As indicated        above, the present invention provides a source of molybdenum in        the form of a tube. The tube can be used in a sputtering process        whereby thin films are deposited on a substrate. In many cases,        the components containing thin-film-deposited substrates are        used in a flat panel display (FPD). The invention provides        molybdenum in a form and with properties which were not        previously available, allowing improvements in the        manufacturability and the performance of the FPD's.        A particular advantage of the present tubular-shaped sputtering        target is its uniform texture. The crystallographic texture of a        tube made according to the invention was determined and is        detailed below.

FIGS. 3A, 3B and 3C show the texture of the sample relative to thelongitudinal (z), radial (ND) and tangential (x) directions,respectively. FIG. 4 shows the top part of FIG. 3B at highermagnification, so the grains can be distinguished. FIG. 5 shows the PoleFigures, and FIG. 6 shows the Inverse Pole Figures.

The material is fully recrystallized and strain-free, as seen by thefact that there is no significant color variation within each grain. Thetexture is well defined, but not very strong (the highest peak is 3.6times random). The most obvious component of texture is 110 parallel tothe longitudinal direction, as seen by the predominant red in FIG. 3A.Another noticeable feature is a sharp 111 peak parallel to the radialdirection. There is only the slightest variation of texture with radius.There is no banding of texture at all. The fine, uniform grain size, andthe uniformity of texture through the thickness of the tube and alongthe length of the tube are features which distinguish the presentinvention from the prior art. These features allow for more uniform filmdeposition during sputtering operations.

Thus, the present invention provides a sputtering target having auniform and fine texture and grain structure. In an embodiment of theinvention, the grain size is at least 22 μm, and in some cases at least45 μm. More importantly, however, the average grain size is not morethan 125 μm, in some cases not more than 90 μm and in other cases notmore than 65 μm. When the grain size is too large, thin films formedfrom sputtering the present sputtering target will not have the desireduniform texture and/or film thickness. The grain size in the presentsputtering target can be any value or range between any values recitedabove.

Embodiments of the invention are also directed to a novel method ofmanufacturing molybdenum sputtering targets, which produces performancesuperior to that which is presently known in the art. This method ofmanufacture involves the use of pure molybdenum powder as a startingmaterial and its consolidation to a substantially fully dense article inthe form of a plate. The inventive plate, which is produced through amulti-directional thermomechanical working process as described below,has a fine, uniform grain size and a texture which is substantiallyuniform throughout the plate. Such plates yield thin films that have therequired purity, and a thickness that is both easily predictable anduniform across the area of the substrate.

In an embodiment of the invention, the plates have a texture that issubstantially free of banding and substantially free of any throughthickness gradient.

In the present multi-directional thermomechanical working process,ammonium dimolybdate is reduced to molybdenum metal powder in hydrogenusing methodologies well known in the art. In an embodiment of theinvention, the ammonium dimolybdate is 99.95%, in some cases 99.9% andin other cases 99.5% pure.

Thus, in a first step I), the molybdenum powder is placed in a mold andpressed at a pressure of at least 100 MPa, in some cases at least 200MPa and in other cases at least 250 MPa. Also, the powder can be pressedat a pressure of up to 275 MPa. The molybdenum powder in the mold can bepressed at any pressure recited above or at pressures ranging betweenany of the pressures recited above.

Further, after the molybdenum powder is pressed in the mold, it issintered at a temperature of at least 1785° C. Also, the powder can besintered at a temperature of up to 2175° C., in some cases up to 2200°C. The pressed molybdenum workpiece can be sintered at any temperaturerecited above or at temperatures ranging between any of the temperaturesrecited above.

In an embodiment of the invention, the pressing is performedisostatically. In another embodiment of the invention, the pressedpowder is sintered in hydrogen. Thus, the molybdenum metal powder can beplaced in a rubber mold, isostatically pressed and the pressed piecethen sintered in hydrogen to form a billet with a cross-sectional areawhich can be from 1.5 to 4, in some cases from 2 to 3, and in aparticular embodiment approximately 2.4 times the size of the intendedtarget cross-sectional area of the eventual sputtering target. In otherwords, the billet has a diameter of D_(o).

The billet is then preheated, prior to extruding, to a temperature of atleast 900° C., in some cases 925° C. and in other cases at least 950° C.Also, the billet can be preheated to a temperature of up to 1260° C., insome cases 1225° C. and in other cases up to 1175° C. The preheatedtemperature can be any value or can range between any values recitedabove.

As shown in FIG. 7, the billet is extruded to form an extruded billethaving a diameter of D₂, such that the ratio of reduction (D_(o):D₂) incross-sectional area is at least 2.5:1, in some cases at least 3:1 andin other cases at least 3.5:1. Also, the ratio of reduction can be up to12:1, in some cases 10:1 and in other cases up to 8:1. The ratio ofreduction can be any value or range between any values recited above.The billet length can be variable.

In an alternative embodiment, rotary forging or hammer forging can beused in place of the extrusion operation to provide a billet with theaforementioned ratio of reduction (D_(o):D₂) in cross-sectional area.

In order to prepare the extruded billet for upset forging, it issubjected to a first heat treatment step. This heat treatment stepgenerally provides stress relief.

The first heat treatment is conducted at a temperature of at least 800°C., in some cases at least 815° C., in some cases at least 830° C. andin other cases at a temperature of at least 850° C. Also, the first heattreatment can be conducted at a temperature up to 960° C., in some casesup to 930° C. and in other cases up to 900° C. The temperature of thefirst heat treatment step can be any value recited above or can rangebetween any values recited above.

The billet is also cut to a length so that it will not buckle. In anembodiment of the invention, the billet is cut to a length such that thebillet's aspect ratio (Length/Diameter) is less than or equal to 2.0, insome cases less than or equal to 1.6.

After the first heat treatment and before upset forging, theheat-treated extruded billet is preheated to a temperature of at least900° C., in some cases at least 925° C., in other cases at least 950°C., in some situations at least 975° C. and in other cases at least1000° C. Also, the heat-treated extruded billet can be preheated to atemperature of up to 1300° C., in some cases up to 1260° C., in othercases up to 1200° C. and in some instances up to 1150° C. Prior to upsetforging, the heat-treated extruded billet can be preheated to anytemperature recited above or can range between any temperature recitedabove.

As shown in FIGS. 8A and 8B, the heat-treated extruded billet issubjected to upset forging such that the ratio of D₂, the heat-treatedextruded billet cross-sectional area, to D_(f), the forged billetcross-sectional area, is from 1:1.5 to 1:3, in some cases 1:1.75 to1:2.5, and in other cases from 1:1.8 to 1:2.25. In an embodiment of theinvention, the ratio of D₂ to D_(f) is approximately 1:2±0.2.Specifically, FIG. 8A shows the billet at the start of the upset forgingprocess and FIG. 8B shows the billet at the end of the upset forgingprocess.

The upset forging of the extruded billet is carried out at a temperatureof at least 800° C., in some cases at least 900° C., in other cases atleast 925° C. and in some instances at least 950° C. Also, the upsetforging of the extruded billet can be carried out at up to 1300° C., insome cases up to 1260° C., in other cases up to 1200° C., in someinstances up to 1100° C. and in other instances up to 1000° C. Theforging temperature allows the billet to be forged to form a forgedbillet having a diameter D_(f) as described above. The forgingtemperature can be any temperature described above or can range betweenany of the temperatures recited above.

After forging, the forged billet is subjected to a second heat treatmentstep. The second heat treatment step is a recrystallization step thatprovides a strain-free equiaxial grain structure. The second heattreatment is conducted at a temperature of at least 1200° C., in somecases at least 1250° C., in some cases at least 1275° C. and in othercases at a temperature of at least 1300° C. Also, the second heattreatment can be conducted at a temperature up to 1400° C., in somecases up to 1375° C. and in other cases up to 1350° C. The temperatureof the second heat treatment step can be any value recited above or canrange between any values recited above.

In an alternative embodiment, the second heat treatment provides stressrelief only and not recrystallization. In this embodiment, the heattreatment is carried out at a temperature of at least 800° C., in somecases 815° C. and in other cases at least 850° C. Also, the heattreatment can be carried out at a temperature of up to 1000° C., in somecases up to 960° C. and in other cases up to 925° C. The temperature ofthe second heat treatment step under this embodiment can be any valuerecited above or can range between any values recited above.

As indicated above, the second heat treatment is applied at atemperature and for a time that provides a billet that has a strain-freeequiaxial grain structure. Thus, after the second heat treatment, abillet is provided that is completely recrystallized and strain free.

As shown in FIG. 9A, material affected during upset forging by thecentering disks (CD) is removed. The material affected by the centeringdisks is not generally usable as target material. Sputtering targets aresliced from the billet according to the orientation shown in FIG. 9B.The entirety of the billet is usable as target once the centering diskaffected material is removed.

In an alternative embodiment as shown in FIGS. 10A and 10B, the upsetforging operation is replaced by a hammer/upset forging such that theratio of D₂, the heat-treated extruded billet cross-sectional area, toD_(f), the forged billet cross-sectional area, is as described above.FIG. 10A shows the billet at the start of the hammer forging operationand FIG. 10B shows the billet after the hammer forging operation. Afterthe hammer forging operation, the billet is given a second heattreatment as described above. In other words, a disc-shaped portion iscut from the heat-treated forged billet to provide a disc-shapedsputtering target.

The grain and texture of the resulting sputtering target is generallyanalyzed using electron backscatter diffraction (EBSD). Because of theabove-described process, the grain and texture from target to target isvery consistent. The targets are typically sampled from the center,mid-radius, and edge on the XZ plane, i.e., the radial-axial plane.

In an embodiment of the present invention, a sputtering target isprovided having a uniform and fine texture and grain structure. In anembodiment of the invention, the grain size is at least 22 μm and insome cases at least 65 μm. More importantly, however, the average grainsize is not more than 125 μm, in some cases not more than 90 μm and inother cases not more than 65 μm as determined by electron backscatterdiffraction. When the grain size is too large and/or non-uniform, thinfilms formed from sputtering the present sputtering target will not havethe desired uniform texture and/or film thickness. The grain size in thepresent sputtering target can be any value or range between any valuesrecited above.

The present invention also provides a method of making a sputteringtarget including the steps, as described above, of:

-   -   I) placing molybdenum powder in a mold and pressing the powder        at the pressures indicated above and sintering the pressed piece        at temperatures indicated above to form a billet having a        diameter of D_(o);    -   II) extruding the billet to form an extruded billet having a        diameter of D₂ such that the ratio of D_(o) to D₂ is as        indicated above;    -   III) applying a first heat treatment to the extruded billet at        the temperatures indicated above;    -   IV) upset forging the extruded billet at the temperatures        indicated above to form a forged billet having a diameter D_(f)        such that the ratio of D_(f) to D₂ is as indicated above;    -   V) applying a second heat treatment to the forged billet at the        temperatures indicated above; and optionally    -   VI) cutting a disc-shaped portion from the heat-treated forged        billet to provide a disc-shaped sputtering target.

Embodiments of the invention provide large molybdenum plates having anon-segmented construction. As used herein, the term “non-segmented”refers to plates made in one piece and not to plates made by combiningor joining two or more plates. Typically, the present plates weigh atleast 300 kg, in some cases at least 350 kg and in other cases at least400 kg. The plates according to the invention include at least 99%, insome cases at least 99.5% and in other cases at least 99.9% by weight ofmolybdenum.

In an embodiment of the invention, the large molybdenum plates have afine, uniform grain size where the average grains are not more than 100μm, in some cases not more than 60 μm, and in other cases not more than20 μm. In this embodiment, the grain size can be at least 5 μm and insome cases at least 10 μm. The grain size can be any value recited aboveor range between any values recited above.

In an embodiment of the invention, the large molybdenum plates include abacking plate to provide support.

In another embodiment of the invention, the large plate has a texturethat is substantially free of banding and substantially free of anythrough thickness gradient.

In an embodiment of the invention, the plates have a rectangularcross-sectional shape and have a length of at least 0.8 m, in some casesat least 1.2 m and in other cases at least 2 m and up to 2.6 m, in somecases up to 3.4 m and in other cases up to 4 m; a width of at least 0.7m, in some cases at least 0.9 m and in other cases at least 1.2 m and upto 1.7 m, in some cases up to 2.0 m and in other cases up to 2.5m; and aheight (thickness) of at least 0.008 m, in some cases at least 0.012 mand in other cases at least 0.018 m and up to 0.020 m, in some cases upto 0.032 m and in other cases up to 0.064 m. The dimensions of therectangular plate can be any of the values recited above and can rangebetween any of the values recited above. In another embodiment of theinvention, the plates have a square cross sectional shape and have alength of at least 0.8 m, in some cases at least 1.0 m and in othercases at least 1.2 m and up to 1.6 m, in some cases up to 2.0, in somesituations up to 2.5 m, and in other cases up to 3.0 m; a substantiallyequal width and height (thickness) of at least 0.008 m, in some cases atleast 0.012 m and in other cases at least 0.018 m and up to 0.020 m, insome cases up to 0.032 m and in other cases up to 0.064 m. Thedimensions of the square plate can be any of the values recited aboveand can range between any of the values recited above.

In another embodiment of the invention, a portion can be cut from theplate to form either a circular or cylindrical cross-sectional shapedportion having a length (thickness) of at least 0.008 m, in some casesat least 0.010 m and in other cases at least 0.012 m and up to 0.018 m,in some cases up to 0.032 m and in other cases up to 0.064 m; and adiameter of at least 0.7 m, in some cases at least 0.9 m and in othercases at least 1.2 m and up to 1.75 m, in some cases up to 2.0 m, inother cases up to 2.5 m, and in some instances up to 3.0 m. Thedimensions of the circular portion can be any of the values recitedabove and can range between any of the values recited above.

As is known in the art and regardless of the particular shape of thesputtering target, when the dimensions of the sputtering target reach asize where support is needed, a backing plate is included with thesputtering target.

In making the large molybdenum plate according to the invention,molybdenum powder is used. The powder is prepared by thermal andhydrogen reduction of ammonium molybdate that is at least 99%, in somecases at least 99.5% and in other cases at least 99.9% pure to producemolybdenum metal powder. The powder is typically screened to produce aparticle morphology and size distribution to sinter. The particle sizetypically has a weight average value of at least 0.1 μm, in some casesat least 0.5 μm, in other cases at least 1 μm, in some instances atleast 5 μm, in other instances at least 10 μm, in some situations atleast 15 μm and in other situations at least 20 μm. Also, the particlesize typically has a weight average value and up to 150 μm, in somecases up to 125 μm, in other cases up to 100 μm, in some instance up to75 μm, in other instances up to 50 μm and in some situations up to 40μm. The particle size of the powder can be any of the values recitedabove and can range between any of the values recited above.

The particle morphology can typically be described as irregularly-shapedagglomerates of fine particles.

The molybdenum powder is poured into a sheet bar mold and jolted/tapped.

The molybdenum powder is then consolidated by cold isostatic pressing(CIP) at a pressure of at least 100, in some cases at least 125 and inother cases at least 150 Mpa. Also, the CIP pressure can be up to 250,in some cases up to 225, and in other cases up to 200 Mpa. The CIPpressure is a pressure sufficient to form a sheet bar. The CIP pressurecan be any value recited above or range between any values recitedabove.

After the CIP process, the sheet bar is sintered at a temperature of atleast 1600° C., in some cases 1650° C. and in other cases at least 1700°C. Also, the sintering temperature can be up to 1800° C., in some casesup to 1750° C. and in other cases up to 1725° C. The sinteringtemperature is a temperature sufficient to form an ingot having adensity of at least 90% of the theoretical density. The sinteringtemperature can be any temperature or range between any temperaturesrecited above.

The sintering is performed for at least 4, in some cases at least 10 andin other cases at least 16 hours. Also, the sintering is performed forup to 32, in some cases up to 24 and in other cases up to 20 hours. Thetime for sintering is a length of time sufficient to achieve at least90% of the theoretical density. The length of time for sintering can beany value recited above or range between any values recited above.

The sintered bar, or ingot, is preheated to a temperature of at least1100° C., in some cases at least 1150° C. and in other cases at least1200° C. Also, the ingot can be preheated to a temperature of up to1450° C., in some cases up to 1350° C. and in other cases up to 1300° C.The ingot can be preheated to any temperature or range between anytemperatures recited above.

The preheated ingot is hot rolled at a temperature of at least 1050° C.,in some cases at least 1100° C. and in other cases at least 1150° C.Also, the ingot can be hot rolled at a temperature of up to 1400° C., insome cases up to 1300° C. and in other cases up to 1250° C. The hotrolling effects a reduction in the thickness and an increase in thelength of the ingot. The hot rolling temperature can be any value orrange between any value recited above.

The reduction achieve from hot rolling can be at least 50%, in somecases 75% and in other cases at least 98% of the thickness of thepre-hot rolled ingot.

Also, the length of the ingot can increase at least 50%, in some casesat least 75% and in other cases at least 150% and can increase up to300%, in some cases up to 400% and in other cases up to 500%. The lengthof the ingot can increase to any value or range between any of thevalues recited above. The thickness of the hot rolled ingot can befurther reduced by subsequent reduction, maintaining the integrity ofthe plate. The subsequent reduction can be at least 10%, in some casesat least 15% and in other cases at least 20% and can be up to 30%, insome cases up to 28% and in other cases up to 25% of the hot rolledingot thickness. The subsequent reduction can be any value or rangebetween any of the values recited above.

During the rolling reduction process, the plates can be reheated tomaintain the temperatures indicated above. Typically, the plates areinspected for integrity throughout the rolling process. Also, the platescan be precision leveled to achieve optimum flatness for subsequentmachining/grinding operations in order to achieve the desired finaldimensions.

The roll reduced ingot is heat treated at a temperature of at least 850°C., in some cases at least 860° C. and in other cases at least 880° C.and can be up to 950° C., in some cases up to 920° and in other cases upto 900° C. This heat treatment step can be carried out any temperatureor range between any of the temperatures recited above.

The roll reduced ingot heat treatment is performed for at least 30minutes, in some cases at least 45 minutes and in other cases at least60 minutes. Also, the heat treatment can be performed for up to 180minutes, in some cases up to 120 minutes and in other cases up to 90minutes. The length of time for the heat treatment can be any valuerecited above or range between any values recited above.

During or after the above-described process, the integrity of an ingotcan be conducted using ultrasonic techniques.

In an embodiment of the invention, in preparing any of the sputteringtargets described above, microalloys can be included in the molybdenumpowder prior to pressing. Non-limiting examples of suitable microalloysinclude those comprising one or more metallic materials selected fromTa, Nb, Cr, W and/or V.

In a particular embodiment of the invention, the microalloy has abody-centered cubic (BCC) structure.

When microalloys are used they are typically processed by adding one ormore metallic materials into the molybdenum powder before the powderpressing stage described above. The described steps in forming ingots orbillets are followed as indicated above.

When microalloys are used, they are included in amounts that provide theparticular properties desired. As such, the metallic materials can beincluded at up to 1000 ppm, in some cases up to 750 ppm, in other casesup to 500 ppm, in some situations up to 300 ppm, in other situations upto 150 ppm, and in some instances up to 75 ppm. Also, when included, themetallic materials can be included at a level of at least 10 ppm, insome cases at least 20 ppm and in other cases at least 25 ppm.

When microalloys are included, they are typically included to provideparticular affects on the molybdenum that is finally produced. As anon-limiting example, the molybdenum can take on a BCC structure byintentionally adding W, V and/or Cr or combinations thereof. These BCCmetallic elements, when included with the molybdenum, create a localizedlattice stress. The stress decreases the energy barrier for (a) atomsleaving the sputtering targets when sputtering (i.e. increasing thesputtering rates of the targets), and (b) the etch of thin film duringphotolithographic processes (for example by either liquid etch or dryetch, such as by plasma etch or reactive etch). When the microalloy isincluded, it is included at a level that provides the above-describedeffect, but not at a level that would compromise any properties of thefilm produced.

Additionally, the present invention provides a method of sputtering,whereby any of the above-described sputtering targets are subjected tosputtering conditions and are thereby sputtered.

Any suitable sputtering method can be used in the present invention.Suitable sputtering methods include, but are not limited to, magnetronsputtering, pulse laser sputtering, ion beam sputtering, triodesputtering, and combinations thereof.

The present invention also provides a method of making a thin filmincluding the steps of:

-   (a) sputtering the above-described sputtering target;-   (b) removing Mo atoms from the target; and-   (c) forming a thin film comprising molybdenum onto a substrate.

In an embodiment of the invention, after (b), a step including supplyinga reactive gas to the Mo can be added. A reactive gas is a gas thatincludes a component that can react with the molybdenum either in agaseous state or once deposited onto a substrate to form a molybdenumcompound. As a non-limiting example, the reactive gas can be oxygen,nitrogen and/or a silicon containing gas.

The thin film applied by the present method can have any desiredthickness. The thickness of the thin film will depend on the end useapplication desired. Typically, the thickness of the thin film can be atleast 0.5 nm, in some situations 1 nm, in some cases at least 5 nm, inother cases at least 10 nm, in some situations at least 25 nm, in othersituations at least 50 nm, in some circumstance at least 75 nm and inother circumstances at least 100 nm. Also, the film thickness can be upto 10 μm, in some cases up to 5 μm, in other cases up to 2 μm, in somesituations up to 1 μm and in other situations up to 0.5 μm. The filmthickness can be any of the stated values or can range between any ofthe values stated above.

The thin film can be or be part of a flat panel display.

Due to the uniformity of grain size and texture through the thickness ofthe molybdenum sputtering targets, the films obtained from such targetshave excellent uniformity.

In a particular embodiment of the invention a very thin film isprovided. In this embodiment, the thin film is at least 100 Å, in somecases at least 250 Å and in other cases at least 500 Å. In thisembodiment, the thin film can be up to 5,000 Å, in some cases up to3,000 Å, in other cases up to 2,500 Å and in some situations up to 2,000Å.

Any suitable substrate may be used in the invention. Suitable substratesfor the thin film used in the flat panel display devices (FPD) include,but are not limited to, flexible foils, plastic substrates, glasssubstrates, ceramic substrates, and combinations thereof The plasticsubstrates include, but are not limited to, polynorbomene, polyimide,polyarylate, polycarbonate, polyethylenenaphthanate (PEN),polyethyleneterephthalate (PET), and the like. A non-limiting example ofa ceramic substrate includes sapphire.

In addition to molybdenum thin films on various substrates, MoO_(x)(oxidation), MoN_(x) (nitridation), MoSi_(x) (silicidation) can also beproduced by reactive sputtering or ion implantation.

The invention encompasses products used in various applications. In oneembodiment, a thin film made in accordance with the invention can beused in thin film transistor (TFT)-liquid crystal display (LCD)applications. Also, in another embodiment, the invention encompasses athin film used in solar cell applications, sensor applications,semiconductor devices and metal gates for

CMOS technology (complementary metal oxide semiconductor). In oneembodiment, the invention is directed to a TFT-LCD device containingmolybdenum thin films that serve as gate electrodes that have excellentuniformity. Another embodiment is directed to thin film solar cellapplications, where the invention encompasses solar cells in which Mothin films function as a back contact for the following illustrativedevice structure: MoO₂ containing front contact/p-layer/junctionlayer/n-layer/Mo back contact, in which the p-layer releases electronswhen it is struck by light, resulting in a lack of electrons, andp-layer is negatively charged.

In sensor applications, an MoO₃ film can be produced by reactivesputtering from a Mo target for use as a gas sensor, such as for ammoniadetection. In another embodiment, the invention encompasses eithermolybdenum or nitrided molybdenum films used as gate devices for CMOSprocesses (complementary metal oxide semiconductor) with a tunable workfunction depending on the nitrogen-doping level.

When improving the picture quality of a FPD, increasing the contrast inbright settings is easier than increasing display brightness. An MoO_(x)film can be used to form a black matrix by reactive sputtering frommolybdenum sputtering target to enhance image contrast. Traditionally,either Cr or CrO₂ target is used to form a black matrix in Flat PanelDisplay, which has both health and environmental concerns.

The invention and various embodiments thereof have been described above.It will be obvious to those skilled in the art that various changes andmodifications may be made therein without departing from the scope ofthe invention as defined in the specification and the appended claims.

1.-110. (canceled)
 111. A method of making a sputtering target, themethod comprising: introducing molybdenum powder into a sheet bar mold;pressing the powder to form a sheet bar; sintering the sheet bar at afirst temperature to form an ingot having a density of at least 90% of atheoretical density; preheating the ingot at a second temperature;rolling the ingot, whereby a thickness of the ingot is reduced, to forma plate; and heat treating the plate at a third temperature.
 112. Themethod of claim 111, wherein the powder is pressed at a pressureselected from the range of 100 MPa to 250 MPa.
 113. The method of claim111, wherein the powder is pressed at a pressure of at least 100 MPa.114. The method of claim 111, wherein pressing the powder comprises coldisostatic pressing.
 115. The method of claim 111, wherein the firsttemperature is at least 1600° C.
 116. The method of claim 111, whereinthe first temperature is selected from the range of 1600° C. to 1800° C.117. The method of claim 111, wherein the sheet bar is sintered for atime period of at least 4 hours.
 118. The method of claim 111, whereinthe second temperature is selected from the range of 1100° C. to 1450°C.
 119. The method of claim 111, wherein the second temperature is atleast 1100° C.
 120. The method of claim 111, wherein rolling the ingotcomprises hot rolling the ingot at a fourth temperature.
 121. The methodof claim 120, wherein the fourth temperature is selected from the rangeof 1050° C. to 1400° C.
 122. The method of claim 120, wherein the fourthtemperature is at least 1050° C.
 123. The method of claim 111, whereinrolling the ingot reduces the thickness of the ingot by at least 50%.124. The method of claim 111, wherein the third temperature is selectedfrom the range of 850° C. to 950° C.
 125. The method of claim 111,wherein the third temperature is at least 850° C.
 126. The method ofclaim 111, wherein the plate is heat treated for a time period of atleast 30 minutes.
 127. The method of claim 111, further comprisingproviding the molybdenum powder by reducing ammonium dimolybdate. 128.The method of claim 111, further comprising pressing an additionalpowder with the molybdenum powder, the additional powder comprising atleast one of tantalum, niobium, chromium, tungsten, or vanadium. 129.The method of claim 128, wherein an amount of the additional powder,relative to a total amount of molybdenum powder and additional powder,is at least 10 ppm.
 130. The method of claim 128, wherein an amount ofthe additional powder, relative to a total amount of molybdenum powderand additional powder, is approximately 1000 ppm or less.
 131. Themethod of claim 111, further comprising attaching at least a portion ofthe plate to a backing plate.
 132. The method of claim 111, wherein theplate has a texture that is substantially free of banding andsubstantially free of any through thickness gradient.
 133. The method ofclaim 111, wherein a grain size of the plate is substantially uniform.134. The method of claim 111, wherein an average grain size of the plateis no more than 100 μm.
 135. The method of claim 111, further comprisingremoving a portion from the plate, a cross-section of the portion beingsubstantially circular or substantially cylindrical.